CN108479801B - Catalyst for synthesizing levulinate and application thereof - Google Patents
Catalyst for synthesizing levulinate and application thereof Download PDFInfo
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Abstract
A catalyst for synthesizing levulinate and application thereof, a preparation method of the catalyst comprises the following steps: (1) weighing calcium-based montmorillonite, adding distilled water and papermaking black liquor, adding acid until the pH of the mixed liquor is 6-7, ball-milling for 3-5 h, and drying to obtain a lignin/montmorillonite composite; (2) carbonizing the lignin/montmorillonite composite at 200-600 ℃ for 1-6 h; (3) mixing the montmorillonite-based lignin carbon material and a sulfonating agent, sulfonating, washing with water, filtering, and drying to obtain the montmorillonite-based lignin carbon composite material. The catalyst of the invention has wide raw material source and low cost, opens up a new way for the comprehensive utilization of the papermaking black liquor, reduces the cost for synthesizing the levulinate ester catalyst, can realize the full utilization of waste resources, can be widely applied to the industries of food additives, essences, spices, chemical reaction intermediates, gasoline, diesel oil additives and the like, and has considerable economic benefit.
Description
Technical Field
The invention belongs to the field of catalytic synthesis, and relates to a catalyst for synthesizing levulinate and application thereof.
Background
The levulinic acid ester compound is a multifunctional compound containing carbonyl and ester groups at the same time, and can generate reactions such as reduction, hydrolysis, condensation and the like, so that various chemicals can be derived. It is not only used in perfume, solvent, oil additive, plasticizer, etc., but also used as important raw material for synthesizing medicine and various chemical products.
The synthesis of levulinate compounds from biomass resources is considered to be one of the most promising methods in the field. The method also comprises the steps of firstly converting biomass into levulinic acid, and then carrying out esterification reaction with alcohol under the action of a catalyst to further generate the levulinic acid ester. Therefore, the key to obtaining high yields of levulinate esters is mainly focused on the catalyst. In early studies, levulinic acid esters were obtained by esterification of levulinic acid with inorganic acids as catalysts, and higher yields were obtained. But the reaction process has the problems of unrecoverable catalyst, difficult product separation, serious environmental pollution and the like. In recent years, there has been some progress in using solid acids as catalysts. At present, the solid acid catalyst reported at home and abroad mainly comprises montmorillonite loaded with dodecaphosphotungstic acid and TiO loaded2/SO4 2-Molecular sieves, strongly acidic resins, and the like. [ Dharne S., Bokade V.V. authentication of leutinic acid to n-butyl leutinic acid over hecteopolic acid supported acid-reameated clean. J. nat. Gas chem., 2011, 20: 18-24. Joyster, Zhaoyang. Molecular sieve supported TiO2/SO4 2-Research on catalytic synthesis of ethyl levulinate, chemical research and application, 2001, 13 (5): 540-. The strong acid cation exchange resin catalyzes and synthesizes the butyl levulinate, Shanghai chemical industry, 2005, 30 (4): 14-16.]Their raw material cost and manufacturing cost are quite high and become one of the factors that influence the advancement of catalytic technologies in this field.
The black liquor for paper making is the waste water produced by the alkaline pulping process (soda process and sulfate process) in paper industry, which contains a large amount of lignin and is black brown, so it is called black liquor. The black liquor contains a large amount of suspended solids, organic pollutants and toxic substances, and the direct discharge of the black liquor into a water body can cause serious pollution.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art and provide a catalyst for synthesizing levulinate and application thereof.
The technical scheme adopted by the invention for solving the technical problems is that the preparation method of the catalyst for synthesizing the levulinate comprises the following steps:
(1) weighing 500 g of calcium-based montmorillonite, adding 1000-2500 mL of distilled water, adding papermaking black liquor, wherein the mass ratio of lignin to the calcium-based montmorillonite in the papermaking black liquor is 1-2: 1, adding acid with the substance amount concentration of less than 2 mol/L (the acid is added and is used for neutralizing NaOH in the papermaking black liquor, and the lignin is easily carbonized due to too high acid concentration) while stirring until the pH value of the mixed liquor is 6-7, ball-milling for 3-5 h, and drying to obtain a lignin/montmorillonite compound;
(2) carbonizing the lignin/montmorillonite composite obtained in the step (1) at 200-600 ℃ for 1-6 h to obtain a montmorillonite-based lignin carbon material;
(3) mixing the montmorillonite-based lignin carbon material obtained in the step (2) with a sulfonating agent according to a mass ratio of 1: 8-15, sulfonating at 80-120 ℃ for 2-6 h, washing with water, and performing suction filtration until the filtrate is dripped with BaCl2And (3) generating no white precipitate in the solution, and drying the solution at the temperature of 100-120 ℃ for 8-12 hours to obtain a finished product, namely a catalyst for synthesizing levulinate ester, namely montmorillonite-based lignin carbon sulfonic acid.
Further, in the step (1), the mass content of lignin in the papermaking black liquor is 15-30%.
Further, in the step (1), the acid is preferably hydrochloric acid, sulfuric acid or nitric acid, and among them, sulfuric acid is most preferable.
Further, in the step (3), the sulfonating agent is at least one of concentrated sulfuric acid, fuming sulfuric acid and chlorosulfonic acid.
The invention relates to an application of a catalyst for synthesizing levulinate, namely an application of a montmorillonite-based lignin carbon sulfonic acid catalyst in synthesizing levulinate, which comprises the following steps: sequentially adding 1.74 g (15 mmol) of levulinic acid and a catalyst which is 2-10% (preferably 6-10%, more preferably 8-10%) of the weight of the levulinic acid into a reaction container provided with a thermometer, a water separator and a reflux condenser pipe, adding alcohol and 2-10 mL of a water-carrying agent according to the molar ratio of the alcohol to the levulinic acid of 1.8-1: 1, and reacting at the reflux temperature of the water-carrying agent for 1-4 hours to obtain the levulinate. After the reaction is finished, the catalyst is recovered by centrifugation and can be reused after being washed by acetone. The levulinate was analyzed by gas chromatography to give a yield.
The water-carrying agent is at least one of benzene, toluene and cyclohexane.
The alcohol is preferably a straight-chain alcohol, and more preferably at least one of n-butanol and n-propanol.
In the application method, the higher the catalyst dosage, the better the catalyst dosage is in principle, but the catalyst dosage is more than 10 percent, the yield is improved in a limited way, and the resource waste is caused.
The inventor researches and discovers that the papermaking black liquor contains a large amount of lignin, the lignin enters a layered structure of calcium-based montmorillonite by mixing calcium-based montmorillonite for ball milling, and the montmorillonite-based lignin carbon sulfonic acid catalyst which is stable, low in cost and high in catalytic activity can be prepared by carbonization and sulfonation.
The catalyst of the invention has wide raw material source and low cost, opens up a new way for the comprehensive utilization of the papermaking black liquor on the one hand, greatly reduces the raw material cost and the manufacturing cost for synthesizing the levulinate ester catalyst, can realize the full utilization of waste resources simultaneously, and the obtained levulinate ester compound can be widely applied to industries such as food additives, essences, spices, chemical reaction intermediates, gasoline, diesel oil additives and the like, and has considerable economic benefit.
Detailed Description
The present invention is further described below by way of examples, but the embodiments of the present invention are not limited thereto. The following description is only exemplary of the invention, and any person skilled in the art may make modifications to the disclosed embodiments by using equivalent variations. Any simple modification or equivalent changes made to the following embodiments according to the technical essence of the present invention, without departing from the technical spirit of the present invention, fall within the scope of the present invention. Unless otherwise specified, the experimental procedures in the following examples are all conventional.
Example 1
The preparation method of the catalyst for synthesizing levulinate of the embodiment comprises the following steps:
(1) push buttonm(lignin):m(montmorillonite) =1:1, weighing 500 g of calcium-based montmorillonite into a reaction kettle, adding 2500 mL of distilled water and 2000g of papermaking black liquor with the mass content of lignin of 25%, adding 1mol/L of sulfuric acid under the stirring condition until the pH value of the mixed liquor is 6-7, ball-milling for 3 h, and drying to obtain a lignin/montmorillonite compound;
(2) weighing lignin/montmorillonite composite, and carbonizing at 400 ℃ for 2 h in a tubular furnace to obtain a montmorillonite-based lignin carbon material;
(3) mixing montmorillonite-based lignin carbon material and 98wt% concentrated sulfuric acid according to the mass ratio of 1:15, and sulfonating for 4 h at 120 ℃. Washing with water to the filtrate and dropwise adding BaCl2No white precipitate was formed in the solution. Drying for 12 h at 100 ℃ to obtain the montmorillonite-based lignin carbon sulfonic acid catalyst.
Example 2: the difference from example 1 is that in step (1)m(lignin):m(montmorillonite) = 2:1, weighing 500 g of calcium-based montmorillonite into a reaction kettle, adding 2500 mL of distilled water and 4000 g of papermaking black liquor with 25% of lignin content, adding 1mol/L of sulfuric acid under the stirring condition until the pH value of the mixed liquor is 6-7, ball-milling for 3 h, and drying to obtain the lignin/montmorillonite composite. Other conditions were the same as in example 1.
Example 3: the difference from the example 1 is that in the step (2), the lignin/montmorillonite composite is weighed and carbonized in a tube furnace for 2 hours at the temperature of 600 ℃, and the montmorillonite-based lignin carbon material is obtained. Other conditions were the same as in example 1.
Example 4: the difference from example 1 is that in step (3), the montmorillonite-based lignocelluloses material and oleum are mixed according to the mass ratio of 1:10, and sulfonated at 120 ℃ for 4 h. Washing with water to the filtrate and dropwise adding BaCl2No white precipitate was formed in the solution. Drying for 12 h at 100 ℃ to obtain the montmorillonite-based lignin carbon sulfonic acid catalyst. Other conditions were the same as in example 1.
Application example 5:
the application of the catalyst for synthesizing levulinate in this example is the application of the pillared montmorillonite-based lignin carbon sulfonic acid catalyst in synthesizing levulinate: in molar ratio of massagen (n-butanol):n(levulinic acid) =1.4:1, levulinic acid 1.74 g (15 mmol), n-butanol 1.55 g (21 mmol), 0.174 g of the catalyst prepared in example 1 was taken; 10mL of cyclohexane was taken as a water-carrying agent.
And sequentially adding levulinic acid and a catalyst into a reaction container provided with a thermometer, a water separator and a reflux condenser pipe, adding n-butanol and a water-carrying agent, and reacting for 4 hours at the reflux temperature (78 ℃) of the water-carrying agent to obtain the butyl levulinate. The yield of butyl levulinate by gas chromatography was 98.6%.
After the reaction is finished, the catalyst is recovered by centrifugation and can be reused after being washed by acetone.
Application example 6: push buttonn (n-butanol):n(levulinic acid) =1.4:1, levulinic acid 1.74 g (15 mmol), n-butanol 1.55 g (21 mmol), 0.174 g of the catalyst prepared in example 2 was added with 10mL of toluene as a water-carrying agent,
levulinic acid and a catalyst are sequentially added into a reaction container provided with a thermometer, a water separator and a reflux condenser pipe, then n-butanol and a water-carrying agent are added, the reaction is carried out for 4 hours at the reflux temperature (110 ℃) of the water-carrying agent, and the yield of the levulinic acid ester is 96.3 percent by gas chromatography.
After the reaction is finished, the catalyst is recovered by centrifugation and can be reused after being washed by acetone.
Application example 7:
push buttonn (n-butanol):n(levulinic acid) =1.4:1, levulinic acid 1.74 g (15 mmol), n-butanol 1.55 g (21 mmol), and 10mL of benzene was added as a water-carrying agent, taking 0.174 g of the catalyst prepared in example 1.
Levulinic acid and a catalyst are sequentially added into a reaction container provided with a thermometer, a water separator and a reflux condenser pipe, alcohol and a water-carrying agent are added, the reaction is carried out for 4 hours at the reflux temperature (80 ℃) of the water-carrying agent, and the yield of the levulinic acid ester is 74.0 percent by gas chromatography.
After the reaction is finished, the catalyst is recovered by centrifugation and can be reused after being washed by acetone.
Application example 8: push buttonn (n-butanol):n(levulinic acid) =1.4:1, levulinic acid 1.74 g (15 mmol), n-butanol 1.55 g (21 mmol), and 0.174 g of the catalyst prepared in example 1 and 8 mL of cyclohexane were used as a water-carrying agent.
Levulinic acid and a catalyst are sequentially added into a reaction container provided with a thermometer, a water separator and a reflux condenser pipe, alcohol and a water-carrying agent are added, the mixture reacts for 4 hours at the reflux temperature (78 ℃) of the water-carrying agent, and the yield of the levulinic acid ester is 99.3 percent through gas chromatography.
After the reaction is finished, the catalyst is recovered by centrifugation and can be reused after being washed by acetone.
Application example 9: push buttonn (n-butanol):n(levulinic acid) =1.4:1, levulinic acid 1.74 g (15 mmol), n-butanol 1.55 g (21 mmol), 0.174 g of the catalyst prepared in example 3 was taken, and 2 mL of cyclohexane was added as a water-carrying agent.
Levulinic acid and a catalyst are sequentially added into a reaction container provided with a thermometer, a water separator and a reflux condenser pipe, alcohol and a water-carrying agent are added, the reaction is carried out for 4 hours at the reflux temperature (78 ℃), and the yield of the levulinic acid ester is 97.1 percent by gas chromatography.
After the reaction is finished, the catalyst is recovered by centrifugation and can be reused after being washed by acetone.
Application example 10: push buttonn (n-butanol):n(levulinic acid) =1.4:1, levulinic acid 1.74 g (15 mmol), n-butanol1.55 g (21 mmol), 0.035 g of the catalyst prepared in example 1 was added with 8 mL of cyclohexane as a water-carrying agent.
Levulinic acid and a catalyst are sequentially added into a reaction container provided with a thermometer, a water separator and a reflux condenser pipe, alcohol and a water-carrying agent are added, the reaction is carried out for 4 hours at the reflux temperature (78 ℃) of the water-carrying agent, and the yield of the levulinic acid ester is 61.4 percent by gas chromatography.
After the reaction is finished, the catalyst is recovered by centrifugation and can be reused after being washed by acetone.
Application example 11:
push buttonn (n-butanol):n(levulinic acid) =1:1, levulinic acid 1.74 g (15 mmol), n-butanol 1.11 g (15 mmol), 0.174 g of the catalyst prepared in example 1 was taken, and 8 mL of cyclohexane was taken as a water-carrying agent.
Levulinic acid and a catalyst are sequentially added into a reaction container provided with a thermometer, a water separator and a reflux condenser pipe, alcohol and a water-carrying agent are added, the mixture reacts for 4 hours at the reflux temperature (78 ℃), and the yield of the levulinic acid ester is 90.2% by gas chromatography.
After the reaction is finished, the catalyst is recovered by centrifugation and can be reused after being washed by acetone.
Application example 12: push buttonn (n-butanol):n(levulinic acid) =1.8:1, levulinic acid 1.74 g (15 mmol), n-butanol 2.00 g (27 mmol), 0.174 g of the catalyst prepared in example 4 was used, and 8 mL of cyclohexane was used as a water-carrying agent.
Levulinic acid and a catalyst are sequentially added into a reaction container provided with a thermometer, a water separator and a reflux condenser pipe, alcohol and a water-carrying agent are added, the mixture reacts for 4 hours at the reflux temperature (78 ℃), and the yield of the levulinic acid ester is 92.9 percent by gas chromatography.
After the reaction is finished, the catalyst is recovered by centrifugation and can be reused after being washed by acetone.
Application example 13: push buttonn (n-propanol):n(levulinic acid) =1.4:1, levulinic acid 1.74 g (15 mmol), n-propanol 1.26 g (21 mmol), and the catalyst prepared in example 1 was used in an amount of 0.174g, add 8 mL cyclohexane as water-carrying agent.
Levulinic acid and a catalyst are sequentially added into a reaction container provided with a thermometer, a water separator and a reflux condenser pipe, alcohol and a water-carrying agent are added, the mixture reacts for 4 hours at the reflux temperature (78 ℃), and the yield of the levulinic acid ester is 98.2% by gas chromatography.
After the reaction is finished, the catalyst is recovered by centrifugation and can be reused after being washed by acetone.
Application example 14: push buttonn (n-butanol):n(levulinic acid) =1.4:1, levulinic acid 1.74 g (15 mmol), n-butanol 1.55 g (21 mmol), and 0.104 g of the catalyst prepared in example 1 and 8 mL of cyclohexane were used as a water-carrying agent.
Levulinic acid and a catalyst are sequentially added into a reaction container provided with a thermometer, a water separator and a reflux condenser pipe, alcohol and a water-carrying agent are added, the mixture reacts for 4 hours at the reflux temperature (78 ℃) of the water-carrying agent, and the yield of the levulinic acid ester is 82.3 percent through gas chromatography.
After the reaction is finished, the catalyst is recovered by centrifugation and can be reused after being washed by acetone.
Application example 15: push buttonn (n-butanol):n(levulinic acid) =1.4:1, levulinic acid 1.74 g (15 mmol), n-butanol 1.55 g (21 mmol), 0.139 g of the catalyst prepared in example 1, and 8 mL of cyclohexane were used as a water-carrying agent.
Levulinic acid and a catalyst are sequentially added into a reaction container provided with a thermometer, a water separator and a reflux condenser pipe, alcohol and a water-carrying agent are added, the mixture reacts for 4 hours at the reflux temperature (78 ℃) of the water-carrying agent, and the yield of the levulinic acid ester is 93.2% by gas chromatography.
After the reaction is finished, the catalyst is recovered by centrifugation and can be reused after being washed by acetone.
Claims (7)
1. A catalyst for synthesizing levulinate is characterized in that the preparation method comprises the following steps:
(1) weighing 500 g of calcium-based montmorillonite, adding 1000-2500 mL of distilled water, adding papermaking black liquid, wherein the mass ratio of lignin to the calcium-based montmorillonite in the papermaking black liquid is 1-2: 1, adding acid with the mass concentration of less than 2 mol/L under stirring until the pH value of the mixed liquid is 6-7, carrying out ball milling for 3-5 h, and drying to obtain a lignin/montmorillonite compound; the mass content of lignin in the papermaking black liquor is 15-30 percent;
(2) carbonizing the lignin/montmorillonite composite obtained in the step (1) at 200-600 ℃ for 1-6 h to obtain a montmorillonite-based lignin carbon material;
(3) mixing the montmorillonite-based lignin carbon material obtained in the step (2) with a sulfonating agent according to a mass ratio of 1: 8-15, sulfonating at 80-120 ℃ for 2-6 h, washing with water, and performing suction filtration until the filtrate is dripped with BaCl2And (3) generating no white precipitate in the solution, and drying the solution at the temperature of 100-120 ℃ for 8-12 hours to obtain a finished product, namely a catalyst for synthesizing levulinate ester, namely montmorillonite-based lignin carbon sulfonic acid.
2. A catalyst for the synthesis of levulinic acid esters according to claim 1, characterised in that in step (1) the acid is hydrochloric acid, sulphuric acid or nitric acid.
3. A catalyst for use in the synthesis of levulinic acid esters according to claim 1 or 2, characterised in that in step (3) the sulphonating agent is at least one of concentrated sulphuric acid, oleum, chlorosulphonic acid.
4. Use of a catalyst for the synthesis of levulinic esters according to any one of claims 1 to 3, characterised in that it comprises the following steps: sequentially adding 1.74 g of levulinic acid and a catalyst which is 2-10% of the weight of the levulinic acid into a reaction container provided with a thermometer, a water separator and a reflux condenser pipe, adding alcohol and 2-10 mL of a water-carrying agent according to the molar ratio of the alcohol to the levulinic acid of 1.8-1: 1, and reacting at the reflux temperature of the water-carrying agent for 1-4 hours to obtain the levulinate.
5. Use of a catalyst for the synthesis of levulinic acid esters according to claim 4, wherein the water-carrying agent is at least one of benzene, toluene, cyclohexane.
6. Use of a catalyst for the synthesis of levulinic acid esters according to claim 4, characterised in that the alcohol is a linear alcohol.
7. Use of a catalyst for the synthesis of levulinic acid esters according to claim 6, characterized in that the alcohol is at least one of n-butanol, n-propanol.
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| CN102112432A (en) * | 2008-06-26 | 2011-06-29 | 波利玛利欧洲股份公司 | Process for production of esters of levulinic acid from biomasses |
| CN106179496A (en) * | 2016-09-21 | 2016-12-07 | 华侨大学 | A kind of preparation method and application of lignin-base hydro-thermal charcoal sulfonic acid catalyst |
| CN106861719A (en) * | 2017-03-07 | 2017-06-20 | 湖南师范大学 | A kind of preparation method of superelevation sulfonic acid density biomass carbon solid acid |
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| CN102112432A (en) * | 2008-06-26 | 2011-06-29 | 波利玛利欧洲股份公司 | Process for production of esters of levulinic acid from biomasses |
| CN106179496A (en) * | 2016-09-21 | 2016-12-07 | 华侨大学 | A kind of preparation method and application of lignin-base hydro-thermal charcoal sulfonic acid catalyst |
| CN106861719A (en) * | 2017-03-07 | 2017-06-20 | 湖南师范大学 | A kind of preparation method of superelevation sulfonic acid density biomass carbon solid acid |
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